EP2597171B1 - Procédé de fabrication de couches cubiques d'oxyde de zirconium - Google Patents

Procédé de fabrication de couches cubiques d'oxyde de zirconium Download PDF

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EP2597171B1
EP2597171B1 EP13154999.0A EP13154999A EP2597171B1 EP 2597171 B1 EP2597171 B1 EP 2597171B1 EP 13154999 A EP13154999 A EP 13154999A EP 2597171 B1 EP2597171 B1 EP 2597171B1
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layer
cubic
layers
oxygen
anode
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EP2597171A1 (fr
EP2597171B8 (fr
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Jürgen RAMM
Beno Widrig
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Oerlikon Surface Solutions AG Pfaeffikon
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Oerlikon Trading AG Truebbach
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0676—Oxynitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0042—Controlling partial pressure or flow rate of reactive or inert gases with feedback of measurements
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3485—Sputtering using pulsed power to the target
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to an anode for a spark evaporation source, a spark evaporation system and a method for operating such a system.
  • the zirconia-based layers are of particular interest in terms of their cubic and / or tetragonal formations, for example in the field of solid electrolyte fuel cell applications.
  • the ionic conductivity of the zirconia-based layers and their thermal stability also allow their use in the field of sensor technology.
  • the document describes a sensor based on a Zr-O layer which is tetragonal or cubic and contains less than 5 mol% admixtures of the monoclinic phase.
  • the reason for the limitation of the monoclinic phase is that it avoids cracking at alternating temperature stress caused by volume changes in the phase transition.
  • the monoclinic phase is avoided by means of stabilizers.
  • Section 101 also describes that a small mean grain size (smaller than 2.5 ⁇ m) in the layer of Advantage is that it behaves more stable to phase transformations.
  • preferred cubic to tetragonal phase ratios are given (400) for cubic phase and (004) and (220) for tetragonal phase.
  • the layers could also be used with advantage in the field of tool coating, in particular the coating of components.
  • the focus is on the design of tribological systems.
  • the adjustable morphology in conjunction with the adjustable hardness of the layers and the simple combination with other oxide layers can be used to optimize the wear of coated workpiece / component and the wear of the counter body.
  • Zirconium oxide-based layers can be described in terms of their composition mainly as Zr-O, Zr-ON, Zr-St-O, Zr-St ON, where St stands for stabilizer elements that contribute to the stabilization of the cubic or tetragonal structure of ZrO2 , Preferably, Y is used as a stabilizer.
  • St stands for stabilizer elements that contribute to the stabilization of the cubic or tetragonal structure of ZrO2
  • Y is used as a stabilizer.
  • zirconia-based Layers known, which will be briefly discussed below.
  • the document describes the difficulties of the layer production in the sintering process and shows a solution approach by reducing the powder size.
  • the layers are not analytically characterized, but the need to demonstrate that it is advantageous for certain applications to make the layer hardness and other mechanical properties of the Zr-O layer adaptable in the tribological system.
  • the Zr-O layers of the US 20040084309 which are suitable for use in a sensor, are also produced in a sintering process.
  • the layers produced by the sintering process tend to be more compact to be considered. They often have to be stabilized (eg by nets) so that the mechanical bond is guaranteed. It depends on the sintering temperature, what structure of the Zr-O is achieved and stabilizers are necessary to achieve the cubic or tetragonal structure.
  • the phases that arise in this process essentially correspond to what can be read from the phase diagram, because the processes are essentially in thermal equilibrium. There are stabilizers that can be sintered only at very high temperatures and are therefore technically difficult or impossible. This limits the possible layer diversity.
  • the "coupling" of the sintered layer to other materials is difficult, since different temperatures are necessary to produce a composite and the material to be bonded limits the temperature range.
  • the layers are brittle, such as porcelain, and it is almost impossible to make multilayer structures.
  • the grain sizes of the materials produced are determined by the starting powder and the sintering process. The simple application of thermal protection layers or metal electrodes can hardly be done in a process.
  • the starting materials are of crucial importance in sintering (grain size) in order to produce high-quality cubic or tetragonal ZrO2 layers. In both cases, great effort must be made to ensure reproducibility in the starting material.
  • An improved manufacturing method should therefore both the Ensure the manufacturing process of the starting material (target) and the temporal consistency of the material quality during the coating process.
  • US 20040022949 discloses a wear protection layer for gas turbines of cubic or tetragonal Zr-O produced by plasma spraying.
  • a treatment in water vapor transforms this layer into the softer monoclinic structure, which converts back into a cubic or tetragonal structure during operation in a gas turbine.
  • the purpose of this additional layer treatment is to design the running-in behavior of the component so that the counter-body is not worn and the soft layer is adapted.
  • the usual stabilizers are used, with yttria (YO) ranging between 0.3 and 20 mol%.
  • the starting materials are of crucial importance for producing high-quality cubic or tetragonal ZrO2 layers.
  • great effort must be made to ensure reproducibility in the starting material.
  • An improved production method should therefore ensure both the production process of the starting material (target) and the temporal consistency of the material quality during the coating process.
  • US_20060171813 describes an application of Zr-O layers to turbine blades.
  • an inner dense layer containing cubic Zr-O or Hf-O is applied another thermal protection layer consisting of a multilayer layer consisting of Zr-O and a metal oxide, for example Ta-O or Nb-O.
  • the layers are deposited by electron beam evaporation.
  • the electron beam evaporation principle allows good adhesion, since it runs under vacuum and the substrate surfaces can be cleaned and activated by plasma treatment.
  • the degree of ionization of the vaporized material in the electron beam evaporation is small, which usually allows only a columnar growth of the layers, which is desirable in thermal protection layers, but is disadvantageous for other applications and in terms of adhesion.
  • the higher degree of ionization of the vapor would also be advantageous from the point of view that it would allow higher energy to be introduced into the layer synthesis via a substrate bias and thus create better conditions for achieving the tetragonal or cubic structures in ZrO 2, even without incorporation of stabilizers. But this has not been achieved here or in other PVD procedures so far.
  • the layers which are produced by the electron beam method usually allow only columnar layer morphology, since the degree of ionization of the metal vapor is too low to increase the mobility at the substrate surface. Of course, this also limits the influence on the layer structure.
  • the care of the melt is another weak point of the process. It must be very carefully and elaborately operated, so that there are no segregations, which then find themselves in the layer composition. Evaporation of alloys is hardly possible, i. one must use the much more difficult process oxide evaporation with oxygen addition in order to achieve halfway stoichiometric layers.
  • IBAD Ion Beam Assisted Deposition
  • an IBAD method which allows the production of strongly (biaxially) oriented YSZ (yttrium stabilized zirconium oxide) on a SiO 2 layer.
  • the figures show for the YSZ the (200) and (400) reflections in the XRD spectrum.
  • the YSZ serves as a growth support for the next following layer, in this application Ce-O, Ru-O and / or LSCO (Lanthanum Strontium Cobald Oxide).
  • the goal is to produce conductive oxides from these materials, which the YSZ substrate needs.
  • examples are given for the preparation of YSZ layers which were deposited at 700 ° C. substrate temperature.
  • the process can be extended to lower temperatures between 450 ° C and 600 ° C.
  • the low process temperature is a desirable property or condition if the layers are to be deposited on already prefabricated substrates, such as Si wafers in the semiconductor industry.
  • the font US_20020031686 reveals in the XRD spectrum the (200) and the (400) reflections of the YSZ in the 2 ⁇ range between 20 ° and 80 °.
  • the IBAD procedure is in US_05872080 described.
  • the IBAD method relies on the bombardment of surfaces, once for the removal of material, on the other hand, to force a certain growth direction of the vacuum-deposited material.
  • the problem with this is that the growth rates in this technique are small and are not suitable for applications in which a lot of material must be deposited over a large area and at low cost.
  • Cyviene describes the problems on the film side in the combined sputtering spark process, which are avoided by the present examples. It is described that the spark discharge with the Zr target in argon with oxygen addition in the synthesized layer does not lead to the cubic or tetragonal phase, but only a monoclinic structure is achieved. Only by adding Y as a stabilizer via the sputtering process can the YSZ be detected in the cubic or tetragonal phase.
  • US_20060009344 It describes the preparation of a Zr-O substrate which comprises both components of monoclinic and cubic structure of Zr-O and which is therefore particularly suitable for producing better adhesion to the actual cubic Zr-O layer.
  • the method is an aerosol "CVD" method. Again emphasis is placed on the grains having sizes between 5 nm and 1000 nm and again the Zr-O is stabilized with YO between 4 mol% and 8 mol%.
  • US 6391164 B1 discloses an anode with a heating coil.
  • the present invention is therefore based on the object of providing processes for the production of zirconium oxide layers, which is not or to a much lesser extent afflicted with the above-described problems of the prior art.
  • the present document is also intended to specify a method for producing zirconium oxide layers, which makes it possible to control the morphology and, in particular, the size of the crystallites, to a large extent and substantially without a major change in the layer composition.
  • zirconium oxide layers which are substantially of cubic and / or tetragonal structure and which, to a much lesser extent, comprise components which are not cubic zirconium oxide or non-tetragonal zirconium oxide compared to the prior art. This applies both to layers which have one or more classical stabilizers and those without classical stabilizers.
  • Classic stabilizers in the context of this description are stabilizers which are present in pure form at room temperature and under normal pressure as solid.
  • Examples of such classical stabilizers are yttrium, magnesium, calcium, scandium and / or the Group IIIA rare earth metals of the Periodic Table.
  • Sr, Ba, Ni, Fe, Co, La, Nd, Gd, Dy, Ce, Al, Bi, Ti, Tb, Eu, Sm may additionally be mentioned here.
  • These stabilizers mentioned can then be found as oxides or mixed oxides in the synthesized Shift again.
  • the term classic stabilizers should also apply to the mixtures of the materials exemplified above.
  • the object is achieved by methods based on reactive spark evaporation in which either the spark current is pulsed and / or a preferably small perpendicular magnetic field is used on the radio target.
  • Generic processes for the production of layers have already been described in the applications US 20070000772 A1 and US 20080020138 A1 described and are assumed to be known here. especially the US 20080090099 A1 also describes the corresponding preparation of ZrO 2 layers. The process is so stable that the radio targets can be operated in reactive gas pressures between 0.1 Pa and 10 Pa.
  • the object is achieved by a method for producing a zirconium oxide-based layer on a deposition substrate, using reactive spark evaporation, with pulsed spark current and / or applying a magnetic field perpendicular to the radio target, wherein a mixed target comprising an elemental zircon and at least one stabilizer is used.
  • the layer is produced in cubic and / or tetragonal crystal structure.
  • one measure is to use a mixed target for the spark evaporation which comprises elementary zirconium and one or more classical stabilizers in the concentration ratio desired in the layer. It has surprisingly been found that such a zirconium stabilizer mixed target can be easily operated by means of a pulsed spark source and / or by means of a low vertical magnetic field under oxygen pressures which are well above 0.1 Pa and can even go up to 10 Pa and beyond.
  • the oxygen partial pressure is therefore selected above 0.1 Pa, preferably at least 10 Pa.
  • the concentration ratios of the mixing target are reproduced essentially in the concentration ratios of the layers applied to the substrates, essentially independently of the oxygen pressure.
  • the concentration ratio of zirconium oxide and stabilizer on the layer at least substantially by the Concentration ratio of elemental zirconium and stabilizer given at the mixing target.
  • the oxygen pressure may be a partial pressure or a total pressure.
  • the cubic and / or tetragonal crystal structure is achieved by selecting the concentration of the stabilizer in the mixed target.
  • the oxygen pressure can be considered and adjusted as with respect to layer composition-free parameters.
  • various experiments have shown that the oxygen pressure or flow can be surprisingly regarded as a significant factor influencing the layer morphology.
  • a method has been shown, which allows the selection of the concentration ratios of the mixing target, a choice of the layer composition and essentially independently, on the choice of oxygen partial pressure, the choice of the layer morphology, such as the size of the crystallites or the question of columnar growth allows , It is also noteworthy that this can happen at relatively moderate substrate temperatures.
  • the oxygen partial pressure is compared to that of reaching cubic and / or tetragonal crystal structure at least substantially free adjusting parameters, used for the specification of the layer morphology.
  • the reactive gas in addition to oxygen, comprises nitrogen.
  • the mentioned object is achieved by a method for producing a zirconium oxide-based layer on a deposition substrate, using reactive sparks evaporation with pulsed spark current and / or applying a magnetic field perpendicular to the radio target, in which a zirconium target of elemental zirconium is used and, in addition to oxygen, nitrogen is used as a reactive gas.
  • the layer is produced in cubic and / or tetragonal crystal structure.
  • the use of classical stabilizers can be dispensed with if, as a second measure, nitrogen is added to the reactive gas. Accordingly, an elemental zirconium target can be used as a target. Without these further measures, ie without nitrogen, monoclinic zirconium oxide layers would now be deposited on the substrates in the course of the spark evaporation.
  • nitrogen and oxygen as the reactive gas results in zircon, oxygen and nitrogen containing layers which are in cubic or tetragonal crystal structure
  • the pressure ratios and gas flow ratios can be selected so that X-ray diffraction spectra of the corresponding layers have clear reflections of the cubically crystallized ZrO 2 .
  • a layer is then produced by adjusting the pressure conditions during spark evaporation, which contains zirconium, oxygen and nitrogen, with cubic and / or tetragonal crystal structure.
  • the oxygen content is preferably adjusted via a gas flow control, while the nitrogen content is selected according to a total pressure control.
  • a coating according to this second example it has been found that, based on cubic zirconium, nitrogen and oxygen-containing layers, it is possible to coat pure ZrO 2 layers, ie completely without stabilizer, which are thin but in cubic crystal structure.
  • the zirconium oxide-based layer is deposited as a pure ZrO 2 layer in a cubic crystal structure, on a cubically crystallized, zirconium, nitrogen and oxygen-containing layer.
  • the second example i. E. the use of nitrogen as additional reactive gas
  • the first example i. the use of a zirconium mixed target containing a classical stabilizer in combination.
  • This makes it possible to produce cubic and / or tetragonal zirconia layers with less stabilizer concentration than usual.
  • the presence of possibly low concentration of classical stabilizer can be used to set the oxygen gas flow to a large extent and thus with the morphology of the applied layer.
  • An issue related to the use of the present example relates to the production of a layered material which has high oxygen ion conductivity and is particularly suitable for solid electrolyte fuel cells.
  • a typical solid electrolyte fuel cell is, for example, in SCSinghal, Recent Progress in Zirconia-Based Fuel Cell for Power Generation, Fifth International Conference on Science and Technology of Zirconia, August 16-22, 1992, Melbourne, Australia s. It can be seen that the actual solid electrolyte layer still has to be provided on both sides with porous electrodes (cathode on the air side, anode on the fuel side) and that it then requires additional "tight" interconnects in order to manufacture a complete fuel cell.
  • the design of the fuel cell is therefore based on a complete layer system that is subjected to intensive thermal cycling. The use of the cell under these conditions places enormous demands on the stability the entire layer package with respect to the prevention of diffusion and stability of the layer structure.
  • This temperature stability includes in particular that there are no or few temperature-induced phase changes in the solid electrolyte. It is also important to control or avoid diffusion processes within the cell in order to counteract "aging phenomena" or performance losses. Of great importance to the stability of the cell is the adaptation of the coefficients of thermal expansion among the various layer materials that make up the cell.
  • Solid electrolyte layer and the overall layer package of the fuel cell there is thus an exemplary use of the previously discussed method for the production of a Festelektolyt harsh in a fuel cell.
  • a zirconium oxide layer is used as the solid electrolyte layer, it should preferably consist predominantly of cubic and / or tetragonal ZrO 2 in order to avoid the phase transformation into a monoclinic structure.
  • classical stabilizers When classical stabilizers are used, their incorporation should preferably be straightforward, and the free choice of classical stabilizers should not be limited by the method of preparation.
  • the stabilizer is chosen freely.
  • Both layer composition and phase composition as well as layer morphology should preferably be able to be varied largely independently of one another by means of parameters of the production method that are easy to regulate.
  • layer composition, phase composition and layer morphology are set at least substantially independently of one another by means of regulating parameters of the evaporation process.
  • Layer morphology and crystal structure of the layer should preferably be producible in a substrate temperature range between 200 ° C and 700 ° C so that they are compatible with common substrate materials and the substrate temperature can be freely chosen to match the different coefficients of expansion throughout Layer package is possible, ie One should preferably be able to choose the substrate temperature so that the tensile and compressive stresses of the individual layers at least partially compensate, for example, in the middle of the operating range.
  • the deposition of the layer takes place at a substrate temperature between 200 ° C. and 700 ° C.
  • the layer is produced as a layer in a layer package.
  • the layer morphology of the solid electrolyte layer should preferably be adjusted from dense Mophology (glassy) to strongly columnar growth.
  • One use of said methods is directed to the preparation of the layer as growth support for a YSZ.
  • the layer is produced with a gradient of the layer composition in the direction of its thickness expansion, preferably the gradient is as follows: From Zr to ZrN, then to ZrO then to ZrO2, with free selectability of morphology and phase.
  • the layer is produced by varying the oxygen / nitrogen content, as a multilayer film.
  • transitions between metal nitride and the various metal oxides play a special role, since both conductive and insulating layers can thus be produced in a material system and the phases can be selected, which is advantageous for both the mechanical and the structural stability of the layer package.
  • the formation of the cubic or tetragonal phase takes place far from the thermal equilibrium state.
  • metal oxides and mixtures may be advantageous, for example, to increase ionic conductivity.
  • the crystallite size of the layer can be adjusted, in particular in the nanometer range. This small crystallite size increases ion transport along the grain boundaries compared to larger grain materials and results in less dependence of ion conductivity on temperature.
  • the solid electrolyte layer systems can be combined with, for example, porous protective layers over the solid electrolyte layer.
  • a method is available, which replaces the high sintering temperatures by a process in which the substrate only temperatures between 200 ° C and 700 ° C are necessary.
  • a method is available, which allows a problem-free coupling of multiple layers with different functionality to the solid electrolyte layer.
  • a process is available which converts powder metallurgy produced material into an intermetallic compound and reactively evaporates and condenses it as a layer on the substrate.
  • a method is available which essentially entails independence from the size of the starting powders.
  • a method is available which is easily transferable to other material systems.
  • a method is available which offers a better possibility of interface formation than that in plasma spraying.
  • a method which utilizes low cost technology, results in a reduction of spatter compared to plasma spraying, and allows for simple process expansion to quaternary oxides.
  • a method which uses targets which can be produced by standard methods, for example in the powder metallurgy method or plasma spraying method, in the compositions desired for the layer.
  • FIG. 19b shows the anode 101 schematically as part of a coating system with spark current source 107 of the coating system and spark cathode 111.
  • the anode 101 comprises a heatable, electrically separated from ground heating coil 103, which is spiked by an additional electrical supply 109.
  • the heating coil 103 of the anode 101 is designed to be electrically insulated from the jacket 105, which can either be grounded or operated in a floating manner and at least partially serves as an anode surface for the spark discharge.
  • the anode 101 is designed such that it deforms during temperature change to such an extent that the oxide layers, which continuously build up on the surface 105 of the anode-forming jacket 105 during coating operation, flake off when the temperature changes.
  • the anode body is formed from sheet metal material.
  • a spark-evaporation plant is operated with such an anode that exposes the anode surface, for at least partial cleaning of a spurious coating, caused by activation / deactivation of the heating coil temperature change, so deforms the anode surface and the spall coating peels off.
  • these self-cleaning anodes can be distributed to guarantee even coating.
  • these anodes can be designed so that they can also be used simultaneously as substrate heating.
  • these anodes can by blinding before direct coating are protected by the spark sources.
  • the treatment chamber is pumped down to a pressure of about 0.01 Pa.
  • a low-voltage arc plasma assisted by radiant heaters is fired between a cathode chamber with hot cathode separated by an orifice and the anodically connected workpieces in an argon-hydrogen atmosphere, the process step being characterized by the following parameters: Electricity of low voltage arc 150 A argon flow 50 sccm Hydrogen flow 300 sccm process pressure 1.4 Pa Substrate temperature 500 ° C stabilizes at approx. process time 45 min
  • the substrates are preferably connected as an anode for the low-voltage arc.
  • the etching of the substrates is carried out in order to achieve an improved layer adhesion to the substrate.
  • the low-voltage arc is operated between the filament and an auxiliary anode.
  • the workpieces are subjected to a negative bias voltage.
  • Typical parameters for this step are: argon flow 60 sccm process pressure 2.4 Pa Electricity of low voltage arc 150 A substrate temperature about 500 ° C process time 30 min bias voltage 200 V (for more intensive etching effects up to 1200 V)
  • the oxide can be deposited directly on the substrate, here is a layer sequence is described, which is particularly suitable for attaching oxides to metallic substrates and the first uses an intermediate layer or support layer (SL) before the actual functional layer (FL) is deposited , This is because a first layer of ZrN is deposited on the substrate.
  • SL intermediate layer or support layer
  • the deposition substrate has a metallic surface, to the effect that a support layer is deposited on the metallic surface, then the layer the support layer, wherein the support layer is preferably made of a metal other than Zr, a nitride or an oxide, preferably ZrN.
  • Total pressure controlled to 3.5 Pa i. Nitrogen is admitted via the flowmeter so that a total pressure of 3.5 Pa always sets in the coating chamber.
  • Substrate bias -60 V (where ranges between -10 V and -1200 V are possible), bipolar pulsed with preferably 36 ⁇ s negative and 4 ⁇ s positive pulse length, which corresponds to a frequency of 25 kHz.
  • substrate temperature about 500 ° C process time approx. 5 min
  • the transition to the actual functional layer takes place, in which oxygen is added via the flowmeter, with the following process parameters: oxygen flow see below process pressure 3.5 Pa (still total pressure controlled) spark current 200 A each for the 4 elementary Zr targets substrate bias -40 V (bipolar) substrate temperature about 500 ° C process time 40 min
  • Example 1 The process described in Example 1 is based on the use of "pure”, ie elementary Zr radio targets without classical stabilizer, which were operated in a pure reactive gas atmosphere, ie without argon but each with either N2 for Zr-N production or with oxygen for Zr-O production.
  • a mixture of nitrogen and oxygen is used.
  • the process is total pressure controlled, ie oxygen addition means nitrogen withdrawal at the same time. In reality this means that with oxygen flows up to about 1000 sccm there are still parts of nitrogen atmosphere in the process chamber.
  • nitrogen was used as decreasing reactive gas addition.
  • the use of exclusively oxygen demonstrably leads to the unwanted monoclinic phase at about 350 sccm oxygen addition at a certain layer thickness.
  • a layer without stabilizer should first be created again (steps E1 and F1).
  • the two Zr (85at%) / Y (15at%) targets were again replaced by two elemental Zr targets, ie 4 Zr targets were operated to produce the intermediate layer.
  • Example 3 it was investigated how a well-adherent interlayer can be made into layer systems which had already been deposited on the substrate with cubic or tetragonal ZrO 2 layers before the coating.
  • these layer systems may have been produced both outside the coating system, for example in another coating process, or also previously in the same coating system.
  • the TiCN layer is a layer known to a person skilled in the art in the field of tool and component coating and their preparation can be assumed to be known to the person skilled in the art.
  • the coupling to the Zr-YO layer takes place in such a way that, just before the end of the TiCN layer, ie in the Ti-spark evaporation phase in the reactive gas mixture of nitrogen and hydrocarbon (for example C2H2), the total pressure is controlled, the two Zrs (92% ) / Y (8at%) - Targets are switched on. After a few minutes, the hydrocarbon gas is then scrapped down and then turned off the Ti targets for TiCN coating. Finally, again after a few minutes, oxygen is added and rattled for the necessary oxygen flow.
  • nitrogen and hydrocarbon for example C2H2
  • Example 1 the layers of Example 1 described in Table 1 are discussed.
  • the evaluation is based on XRD measurements under grazing incidence of 1, which, with a total layer thickness of the investigated layers of approximately 5 ⁇ m, almost excludes or strongly suppresses the influence of the layer area close to the substrate and thus of the SL.
  • these multilayer systems can also be synthesized in the area of oxygen flux, where the transition between nitrogen stabilization and monoclinic phase formation is taking place, thus creating a multilayer structure between cubic and tetragonal phases of ZrO2 (with proportions of cubic Zr (O, N) ) with and without nitrogen build up.
  • the condition for this, however, is that those layers are kept so thin without nitrogen that no folding into the monoclinic phase takes place.
  • Figure 6a (Sample 780), although the entire layer was made with an oxygen flux of 400 sccm, shows a morphology change after about 1.7 ⁇ m of FL from a dense to a columnar structure. This change is accompanied by the phase change of the cubic or tetragonal structure monoclinic structure.
  • yet another aspect of this process approach can be meaningful for the application: the possibility of a ZrN layer, the Zr-O layers gradient connected to the underlying substrate or layer system well, because so good adhesion to metallic substrates or layers can be achieved and a layer growth based on only one material system can be realized.
  • FIGS. 1b, 4b and 6b show the intimate bond of the approximately 500 nm thick ZrN intermediate layer (SL) to the functional layer (FL), while FIG. 18b indicates significantly poorer adhesion, since the ramp into the high oxygen content of ZrO2 is only very short was held.
  • the layer did not show any Nitrogen content in the layer after ERDA, ie the N content is less than 1 at%. This too is approximately consistent with the samples from Example 1, in which no more N was found in the layer at 400 sccm.
  • the morphology of the layer ( Fig. 7 ) is also comparable to that of Sample 780, at least in the near-surface region, and shows columnar structure.
  • Example 3 Zr-Y-O- (N) layers described in Table 4 were prepared.
  • a "non-material" layer namely TiCN was chosen as the intermediate layer (SL).
  • the transition to the Zr-Y-O-N layer was again driven by the total pressure control. However, this time Zr (92at%) - Y (8at%) targets were used.
  • Figure 15 shows the SEM fracture cross-section of a thick Zr (Y8at%) O 2 layer (sample 493) with tetragonal structure, deposited on a chromium-chromium oxide intermediate layer.
  • Zr (92at%) / Y (8at%) targets were used and coated with a very high oxygen flux of 1500 sccm. In this process, no total pressure control was used, but the evaporation was done by the Zr (92at%) / Y (8at%) targets with constant oxygen flux.
  • an oxide can also be used as an intermediate layer, here the chromium oxide, to bind "related" materials together. This may be useful where, for example, the thermal expansion coefficients have to be adjusted to each other, many of which are similar to the oxides.
  • the high oxygen flux transforms the column structure into an even less dense morphology with high porosity and correspondingly large surface area.
  • Such a surface is particularly well suited for sensor applications, as it allows both faster diffusion of the species to be detected contributes and also increases the sensitivity.
  • the XRD spectrum (not shown) shows the Bragg peaks of the tetragonal structure with proportions of the cubic phase, and shows that the tetragonal or cubic phase can also be produced without the total pressure control in the nitrogen.
  • Figure 16 shows the microstructure of a ZrO2 layer made of elemental Zr targets and also with a high oxygen flux of 600 sccm.
  • the interface selected was a thin TiCN of about 500 nm. Again, only the oxygen flow was regulated and not the background pressure with nitrogen background pressure.
  • the layer has the monoclonal phase. Although it does not have the preferred tetragonal or cubic structure, it is suitable for protecting substrates, especially in conjunction as a run-in layer at higher temperatures, so as not to wear the counterpart body.
  • Figure 17a and b show the comparison of ZrO2 layers deposited on a thicker TiCN layer of about 3.5 ⁇ m, with 17a (sample 767) after US 20080020138 A1 However, 17b (sample 769) was pulsed as it was in US 20070000772 A1 is described. Elemental Zr targets were used. The microstructure of the layers shows a clear difference. There is more crystalline growth at 17b. For both layers, the XRD spectra (not shown) indicate the monoclinic phase.
  • Figure 18a and b show a further SEM analysis of a fracture on a sample in which on a thick CrN layer, a Zr-YO functional layer was deposited using Zr (92at%) / Y (8at%) targets. Again, a Cr-N-Zr-Y transition was chosen and then added to the nitrogen total pressure control at 3.5 Pa, 600 sccm oxygen. The morphology of the layer is very porous and therefore has a lot of layer surface. The tetragonal phase dominates in the XRD spectrum, whereby cubic parts can not be excluded.
  • the process differs particularly clearly from other methods of producing ZrO 2 (cubic and / or tetragonal) by the simple starting material and by the possibility of influencing or specifically producing the layer properties, in particular the phase composition of the layer, via this starting material.
  • the difference to the sintering process in which the materials are in powder form and are joined together under high temperatures.
  • the high temperatures are necessary to produce the desired material in the sintering process and depend very much on the additions of foreign materials, for example the stabilizer materials and their concentration. Some materials can not be produced or only in small quantities, since very high sintering temperatures are necessary. This limits both the variety of materials and it also limits the cost-effectiveness.
  • the sputtering process while less problematic than electron beam evaporation, involves the evaporation of alloys, but complicated control of the reactive gas requires oxygen to avoid target poisoning.
  • Methods that combine sputtering with sputtering and use elementary targets also solve this problem unsatisfactorily. They can not be operated in pure sour gas reactive gas, because then on the one hand, the sputtering target and on the other hand poisoned the radioactive target and the anode of the spark discharge is covered with an oxide layer and interrupts the discharge.
  • blending targets are used to make the Zr-Y-O2 films.
  • These targets can be produced in known technology, for example by powder metallurgy in the HIP process. With this method, it is possible to densify materials of very different melting points without the need for fusion as in sintering. The materials still exist as separate materials in the target after the process.
  • An advantage of the method according to one embodiment is that these separately present materials alloy with one another during operation in the oxygen or in the nitrogen-oxygen mixture under the action of the spark moving on the target. Since the temperatures in the spark point can be some 1000 ° C, both refractory materials such as Zr with various concentrations of stabilizers, for example with Y between 1at% and 25at% can melt on the target surface immediately before the transition to the vapor phase.
  • the crystallite size can be controlled via such easily accessible process parameters as oxygen flow, substrate temperature, and through the choice of intermediate layers.
  • the targets to be used for the process can also be produced by plasma spraying by using organometallic gases as precursors for depositing the metallic layer components on a target surface.
  • organometallic gases as precursors for depositing the metallic layer components on a target surface.
  • the advantage of this target production process is that only one alloy is deposited over the concentration of the precursors.
  • the disadvantage here is the higher porosity of the plasma-sprayed targets compared to those produced in the HIP process, but which is basically dominated in the present process under pure oxygen atmosphere.
  • alloyed radio targets provide unsurpassed reproducibility in the starting material and the combination of the operation of the targets under oxygen atmosphere under the constraints of quasi-free selectability of the nitrogen-oxygen reactive gas mixture allows both the adaptation of the layer morphology as also the specification of the shift phases.
  • the method of reactive spark evaporation of elementary Zr or / and mixed targets of Zr optionally with the addition of other materials such as stabilizers St, for example Y, is suitable for a simple and inexpensive synthesis of cubic or tetragonal ZrO2 or Zr-St oxide.
  • the method allows the use of targets with a concentration ratio corresponding to the desired layer composition.
  • targets can be produced inexpensively, for example, by hot isostatic pressing (HIP) or plasma spraying.
  • HIP hot isostatic pressing
  • plasma spraying the desired metallic alloy can already be deposited to the target, for example in the ratio Zr96 / Y4 Zr92 / Y8, Zr90 / Y10, Zr85 / Y15.
  • the method allows the combination with the synthesis of different layer materials in the same coating system and in the same process step.
  • the method allows graded transitions between different materials for the purpose of improved adhesion with each other, the adaptation of the layer properties and the targeted adaptation of the layer properties such as morphology, crystallite size, crystal structure or phase composition.
  • the use of a spark anode, caused by cycles of thermal cycling (switching on and off) in conjunction with the resulting mechanical deformations that cause the oxide layers to flake off lead, is held with advantage, contributes to the stabilization of the spark evaporation in an oxygen atmosphere.
  • the addition of stabilizers to the target in a particular concentration essentially results in a synthesized layer of the same concentration, i. no control effort is necessary as is the case with the evaporation of the materials from separate elemental targets.
  • the concentration of the stabilizers essentially determines the phases of the synthesized layer or its phase composition.
  • the crystallite size and morphology of the layer can be controlled via the oxygen flux and the substrate temperature, i. that the phases are independent of the oxygen flow over a wide range.
  • the combination of using elemental Zr targets and alloy targets containing solid stabilizers in addition to Zr also allows for graded transitions between Zr-O layers and Zr-YO layers in which the Y content of the layer is between 0 and Y content of the alloy target can be varied or, of course, in the opposite direction.
  • Example is the synthesis a cubic ZrO2 layer containing stabilizers, and then a graded transition to zirconia takes place without stabilizers, ie from a certain thickness without stabilizers, the hard cubic structure is connected to that of the soft monoclinic structure, which then serve as an inlet layer, for example can.
  • the method allows the incorporation of stabilizing materials via the gas phase, for example the nitrogen example discussed in detail.
  • the incorporation of these materials can also be extended by adding additional reactive gases (to nitrogen and / or oxygen), which then incorporate equally into the layer. Examples include: hydrocarbons, silanes, hydrogen, boranes, cyano compounds.
  • additional reactive gases to nitrogen and / or oxygen
  • examples include: hydrocarbons, silanes, hydrogen, boranes, cyano compounds.
  • the addition of such further gases can also be carried out to pure oxygen reactive gas, if no total pressure control of the nitrogen background is carried out.
  • the possibilities of influencing the layer morphology and the phase composition also allow the setting of mechanical properties such as layer hardness and toughness.
  • alloy targets in contrast to the prior art, substantially does not result in segregation of the target components in the layer, i.
  • the target composition is also found essentially in the layer, and provides crystallite sizes in the layer which are independent of the crystallite size in the target material.
  • the process significantly reduces the spattering of the target material as it does with other processes by largely converting the powder in the starting material (target) to intermetallic compounds at the target surface.
  • the crystallite size of the layer is adjustable independently of the grain size used of the powder used in the target.
  • the vacuum process in conjunction with the use of pure powder-made targets, reduces contaminants of the layer to less than 1% by other materials.
  • the alloying process on the target usually proceeds rapidly, affecting interlayer quality i.a. Not. But it can also, if necessary, be separated from the layer deposition on the substrates by the use of diaphragms in front of the target.
  • the layers may have cubic or teragonal phases, although they do not contain proportions of "classical stabilizers", e.g. Y, in the layer have.
  • the cubic or tetragonal phase of the layer can be grown on a cubic underlay.
  • cubic phase underlayers which essentially contain Zr as a metallic constituent, e.g. cubic ZrN, cubic ZrO or cubic or tetragonal ZrO2.
  • the layers of different phase or phase composition can be a graded transition to Have underlayer, which is reflected in an NO gradient and its depth profile can be detected within the layer, for example by means of SIMS.
  • the phase of the layer or its phase composition is substantially maintained in the substrate temperature range between 200 ° C and 700 ° C. It only changes the crystallite size, i. at low temperature, the layer is fine crystalline or amorphous and receives larger crystallites at higher substrate temperature. In this way, layers can be produced both with crystal sizes in the nanometer range, but also crystallite sizes up to 100 nm and above.
  • the synthesized ZrO2 layers are substoichiometric in oxygen, detectable by RBS analysis. It should be noted here that this RBS analysis also takes into account that the elements Zr and Y in the spectrum are readily inseparable, but that this was taken into account in the estimation, as well as the different valence of Zr (ZrO2) and Y (Y2O3) in the oxide formation, so that even taking into account these effects still sub stoichiometry of the oxygen with respect to Zr is present.
  • the layers have the metallic spatter typical of spark evaporation, consisting of predominantly refractory Zr and not fully oxidized.
  • the layers produced by the present process are very well suited for a wide variety of applications.
  • such layers produced by means of spark evaporation are preferably used as solid electrolytes in fuel cells.
  • the layers Due to the good ion-conducting properties, the layers can be used very well in sensors.
  • the exemplified layers form very good thermal barrier layers and thus can be used to protect tools and components such as turbine blades and turbochargers.
  • the zirconium oxide layers are advantageously used as a high temperature antifuse layer for tools and, in particular, for cutting tools such as e.g. Inserts and drills can be used.
  • the layer system comprises a zicon oxide layer in a monoclinic phase, it can be used as a friction-reducing layer in high-temperature applications.
  • the phase of the layer can be changed, for example, from cubic to monoclinic.
  • the crystallite size can be changed in a targeted manner by changing the oxygen flow and / or the substrate temperature.
  • multilayer structures with bilayers in the nanometer range can be produced in the context of the method.
  • bilayers are ZrN / ZrOx transitions, ZrO / ZrO2 transitions, ZrO2 (trigonal or cubic) / ZrO2 (monoclinic) transitions.
  • the total pressure in the spark evaporation system can be chosen so high that due to the greatly reduced average free path length of a large part of the material does not land on a substrate to be coated, but remains as a powder in the chamber.
  • a sacrificial layer for example, a thin graphite layer, which can be sprayed easily.

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Claims (8)

  1. Anode pour une source d'évaporation par arc, comprenant :
    - un corps d'anode avec une surface anodique,
    - le long de la surface anodique un filament de chauffage qui est isolé électriquement du corps d'anode,
    - des raccordements isolés électriquement du corps d'anode pour le filament de chauffage,
    l'anode étant conçue de telle sorte que la surface anodique, pour le nettoyage au moins partiel d'un revêtement parasite, peut être exposée à un changement de température provoqué par l'activation/désactivation du filament de chauffage et se déforme ainsi de telle sorte que le revêtement parasite s'écaille.
  2. Anode selon la revendication 1, caractérisée en ce que le corps d'anode est formé d'un matériau en tôle.
  3. Anode selon l'une des revendications 1 ou 2, caractérisée en ce que le filament de chauffage est réalisé sous la forme d'un chauffage de substrat.
  4. Installation d'évaporation par étincelle comprenant une anode selon l'une des revendications 1 à 3.
  5. Installation d'évaporation par étincelle selon la revendication 4 comprenant plusieurs anodes.
  6. Installation d'évaporation par étincelle selon la revendication 4 ou 5, caractérisée en ce qu'avant l'anode ou les anodes, il est prévu des obturateurs pour protéger contre le revêtement.
  7. Procédé pour faire fonctionner une installation d'évaporation par arc avec une anode selon la revendication 1 ou 2, caractérisé en ce que l'on expose la surface anodique, pour nettoyer au moins partiellement d'un revêtement parasite, à un changement de température provoqué par l'activation/désactivation du filament de chauffage, de sorte que la surface anodique se déforme et le revêtement parasite s'écaille.
  8. Procédé selon la revendication 7, caractérisé en ce que le filament de chauffage permet de chauffer un substrat devant être recouvert par évaporation par arc.
EP13154999.0A 2009-09-25 2010-09-24 Procédé de fabrication de couches cubiques d'oxyde de zirconium Active EP2597171B8 (fr)

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RU2551739C2 (ru) 2015-05-27
WO2011036246A3 (fr) 2011-06-16
EP2597171A1 (fr) 2013-05-29
DE202010017875U1 (de) 2012-11-28
CN102666908A (zh) 2012-09-12
EP2480699A2 (fr) 2012-08-01
US9945024B2 (en) 2018-04-17
KR101850667B1 (ko) 2018-05-31
BR112012006570B1 (pt) 2019-07-16
EP2480699B1 (fr) 2017-12-06
EP2597171B8 (fr) 2019-08-21
CN102666908B (zh) 2020-07-21
RU2012116532A (ru) 2013-10-27
ES2749354T3 (es) 2020-03-19
CA2775044C (fr) 2018-04-24
JP2013506049A (ja) 2013-02-21
US20130153408A1 (en) 2013-06-20
WO2011036246A2 (fr) 2011-03-31
CN107299313A (zh) 2017-10-27
JP2015110840A (ja) 2015-06-18
KR20120080612A (ko) 2012-07-17
ES2660745T3 (es) 2018-03-26
CA2775044A1 (fr) 2011-03-31
KR20170073734A (ko) 2017-06-28
BR112012006570A2 (pt) 2017-08-29

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